Chapter 8: Major Elements

“Wet-chems”: gravimetric/volumetric
 Chapter 8: Major Elements
Modern Spectroscopic Techniques

Figure 8.1. The geometry of typical spectroscopic instruments. From Winter (2001) An Introduction to
Igneous and Metamorphic Petrology. Prentice Hall.
 Element Wt % Oxide Atom %
O 60.8
Si 59.3 21.2 Abundance of the elements
Al 15.3 6.4
Fe 7.5 2.2
in the Earth’s crust
Ca 6.9 2.6
Mg 4.5 2.4
Na 2.8 1.9

Major elements: usually greater than 1%

SiO2 Al2O3 FeO* MgO CaO Na2O K2O H2O
Minor elements: usually 0.1 - 1%
TiO2 MnO P2O5 CO2
Trace elements: usually < 0.1%
everything else
 A typical rock analysis
Wt. % Oxides to Atom % Conversion
Oxide Wt. % Mol Wt. Atom prop Atom %
SiO2 49.20 60.09 0.82 12.25
TiO2 1.84 95.90 0.02 0.29
Al2O3 15.74 101.96 0.31 4.62
Fe2O3 3.79 159.70 0.05 0.71
FeO 7.13 71.85 0.10 1.48
MnO 0.20 70.94 0.00 0.04
MgO 6.73 40.31 0.17 2.50
CaO 9.47 56.08 0.17 2.53
Na2O 2.91 61.98 0.09 1.40
K2O 1.10 94.20 0.02 0.35
H2O+ 0.95 18.02 0.11 1.58
(O) 4.83 72.26
Total 99.06 6.69 100.00

Must multiply by # of cations in oxide 

 Table 8-3. Chemical analyses of some
representative igneous rocks
Peridotite Basalt Andesite Rhyolite Phonolite
SiO2 42.26 49.20 57.94 72.82 56.19
TiO2 0.63 1.84 0.87 0.28 0.62
Al2O3 4.23 15.74 17.02 13.27 19.04
Fe2O3 3.61 3.79 3.27 1.48 2.79
FeO 6.58 7.13 4.04 1.11 2.03
MnO 0.41 0.20 0.14 0.06 0.17
MgO 31.24 6.73 3.33 0.39 1.07
CaO 5.05 9.47 6.79 1.14 2.72
Na2O 0.49 2.91 3.48 3.55 7.79
K2O 0.34 1.10 1.62 4.30 5.24
H2O+ 3.91 0.95 0.83 1.10 1.57

Total 98.75 99.06 99.3 99.50 99.23

 CIPW Norm

Mode is the volume % of minerals seen

Norm is a calculated “idealized”
mineralogy
 Variation Diagrams
How do we display chemical data in a meaningful way?
Bivariate
(x-y)
diagrams
Harker
diagram
for
Crater
Lake

Figure 8.2. Harker variation

diagram for 310 analyzed
volcanic rocks from Crater Lake
(Mt. Mazama), Oregon Cascades.
Data compiled by Rick Conrey
(personal communication).
Bivariate
(x-y)
diagrams
Harker
diagram
for
Crater
Lake

Figure 8.2. Harker variation

diagram for 310 analyzed
volcanic rocks from Crater Lake
(Mt. Mazama), Oregon Cascades.
Data compiled by Rick Conrey
(personal communication).
 Ternary Variation Diagrams
Example: AFM diagram
(alkalis-FeO*-MgO)

Figure 8.3. AFM diagram for

Crater Lake volcanics, Oregon
Cascades. Data compiled by Rick
Conrey (personal
communication).
Models of Magmatic Evolution
Table 8-5. Chemical analyses (wt. %) of a
hypothetical set of related volcanics.

Oxide B BA A D RD R
SiO 2 50.2 54.3 60.1 64.9 66.2 71.5
TiO 2 1.1 0.8 0.7 0.6 0.5 0.3
Al2O3 14.9 15.7 16.1 16.4 15.3 14.1
Fe2O3* 10.4 9.2 6.9 5.1 5.1 2.8
MgO 7.4 3.7 2.8 1.7 0.9 0.5
CaO 10.0 8.2 5.9 3.6 3.5 1.1
Na 2O 2.6 3.2 3.8 3.6 3.9 3.4
K2O 1.0 2.1 2.5 2.5 3.1 4.1
LOI 1.9 2.0 1.8 1.6 1.2 1.4
Total 99.5 99.2 100.6 100.0 99.7 99.2
B = basalt, BA = basaltic andesite, A = andesite, D = dacite,
RD = rhyo-dacite, R = rhyolite. Data from Ragland (1989)
Figure 8.6. Stacked variation diagrams of
hypothetical components X and Y (either
weight or mol %). P = parent, D = daughter,
S = solid extract, A, B, C = possible
extracted solid phases. For explanation, see
text. From Ragland (1989). Basic Analytical
Petrology, Oxford Univ. Press.
Harker diagram
 Smooth trends
 Model with 3 assumptions:

1 Rocks are related by FX

2 Trends = liquid line of
descent
3 The basalt is the parent
magma from which the others
are derived

Figure 8.7. Stacked variation diagrams of

hypothetical components X and Y (either
weight or mol %). P = parent, D = daughter,
S = solid extract, A, B, C = possible
extracted solid phases. For explanation, see
text. From Ragland (1989). Basic Analytical
Petrology, Oxford Univ. Press.

Extrapolate BA  B and
further to low SiO2

K2O is first element to  0
(at SiO2 = 46.5)

46.5% SiO2 is interpreted

to be the concentration in
the bulk solid extract and
the blue line  the
concentration of all other
oxides

Figure 8.7. Stacked variation diagrams of

hypothetical components X and Y (either
weight or mol %). P = parent, D = daughter,
S = solid extract, A, B, C = possible
extracted solid phases. For explanation, see
text. From Ragland (1989). Basic Analytical
Petrology, Oxford Univ. Press.
 Extrapolate the other curves
back BA  B  blue line and
read off X of mineral extract

Results:
Remove plagioclase, olivine,
pyroxene and Fe-Ti oxide

Oxide Wt% Cation Norm

SiO2 46.5 ab 18.3

TiO2 1.4 an 30.1
Al2O3 14.2 di 23.2
Fe2O3* 11.5 hy 4.7
MgO 10.8 ol 19.3
CaO 11.5 mt 1.7
Na2O 2.1 il 2.7
K2O 0
Total 98.1 100
Then repeat for each increment BA  A etc.
Figure 8.8.
Variation
diagram on a
cation basis for
the fractional
crystallization
of olivine,
augite, and
plagioclase to
form BA from
B (Table 8-6).
From Ragland
(1989). Basic
Analytical
Petrology,
Oxford Univ.
Press.
Figure 8.9. Equilateral triangle showing the solution to the bulk mineral extract (shaded area)
best fitting the criteria for the variation diagrams in Figure 8-8. From Ragland (1989). Basic
Analytical Petrology, Oxford Univ. Press.
 Magma Series
Can chemistry be used to distinguish families
of magma types?
Early on it was recognized that some
chemical parameters were very useful in
regard to distinguishing magmatic groups

 Total Alkalis (Na2O + K2O)

 Silica (SiO2) and silica saturation
 Alumina (Al2O3)
Alkali vs. Silica diagram for Hawaiian volcanics:
Seems to be two distinct groupings: alkaline and subalkaline

Figure 8.11. Total

alkalis vs. silica
diagram for the alkaline
and sub-alkaline rocks
of Hawaii. After
MacDonald (1968).
GSA Memoir 116
 The Basalt Tetrahedron and the Ne-Ol-Q base

Alkaline and subalkaline fields are again

distinct

Figure 8.12. Left: the basalt tetrahedron (after Yoder and Tilley, 1962). J. Pet., 3, 342-532. Right: the base of the
basalt tetrahedron using cation normative minerals, with the compositions of subalkaline rocks (black) and
alkaline rocks (gray) from Figure 8-11, projected from Cpx. After Irvine and Baragar (1971). Can. J. Earth Sci., 8,
 Thermal divide separates the silica-saturated
(subalkaline) from the silica-undersaturated
(alkaline) fields at low pressure

Cannot cross this divide by FX, so can’t derive

one series from the other (at least via low-P FX)

1713
Liquid

Thermal
Divide Tr + L

Ne + L Ab + LAb + L
1070 1060
Ne + Ab Ab + Tr
Ne Ab Q
AFM diagram: can further subdivide the subalkaline
magma series into a tholeiitic and a calc-alkaline series

Figure 8.14. AFM diagram showing the distinction F

between selected tholeiitic rocks from Iceland, the Mid-
Atlantic Ridge, the Columbia River Basalts, and Hawaii
(solid circles) plus the calc-alkaline rocks of the Cascade
volcanics (open circles). From Irving and Baragar
(1971). After Irvine and Baragar (1971). Can. J. Earth
h o l ei
Sci., 8, 523-548. T it

ic
Calc-alkaline

A M
Figure 18.2. Alumina saturation classes based on the molar proportions of Al2O3/(CaO+Na2O+K2O) (“A/CNK”) after
Shand (1927). Common non-quartzo-feldspathic minerals for each type are included. After Clarke (1992). Granitoid
Rocks. Chapman Hall.
Figure 8.10
a. Plot of CaO (green) and (Na2O +
K2O) (red) vs. SiO2 for the Crater
Lake data. Peacock (1931) used the
value of SiO2 at which the two curves
crossed as his “alkali-lime index”
(dashed line).
b. Alumina saturation indices (Shand,
1927) with analyses of the
peraluminous granitic rocks from the
Achala Batholith, Argentina (Lira and
Kirschbaum, 1990). In S. M. Kay and
C. W. Rapela (eds.), Plutonism from
Antarctica to Alaska. Geol. Soc. Amer.
Special Paper, 241. pp. 67-76.
Fig. 8.17. After Le Maitre (1976)
J. Petrol., 17, 589-637.
 A world-wide survey suggests that there may be
some important differences between the three series

Characteristic Plate Margin Within Plate

Series Convergent Divergent Oceanic Continental
Alkaline yes yes yes
Tholeiitic yes yes yes yes
Calc-alkaline yes

After Wilson (1989). Igneous Petrogenesis. Unwin Hyman - Kluwer

Figures I don’t use

Figure 8.4.  Pearce element diagram of 0.5(Fe + Mg)/K vs. Si/K for two Hawaiian picritic magma suites.
From Nicholls and Russell (1990).
Figure 8.5.  Pearce
element diagrams
for basalts (dark
circles) and picrites
(light circles)
erupted from
Kilauea, Hawaii,
between
November, 1967
and August, 1968.
After Nicholls
(1990).
Figure 8.15.  Plot
of wt.% Al2O3 vs.
anorthite content
of the normative
plagioclase,
showing the
distinction
between the
tholeiitic and
calc-alkaline
series. From
Irvine and
Baragar (1971).
Figure 8.16.  
Wt.% K2O vs. Na2O
diagram subdividing the
alkaline magma series into
High-K-, K-, and Na-sub-
series. After Middlemost
(1975). Copyright © with
permission from Elsevier
Science.